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United States A Patent POLYMERS OF N-Z-NORCAMPHANYL- ACRYLAMIDES John R. Caldwell and Edward H. Hill, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application August 4, 1954, Serial No. 447,900

20 Claims. (Cl. 260-821) This invention relates to poiymeric materials containing N-Z-norcamphanylacrylamide or N-Z-norcamphanylmethacrylamide, and to the preparation of such polymers.

In the preparation of films, fibers, molded objects and the like from polymeric materials, it is desirable that the polymers possess a relatively high melting pointor softening or sticking temperature. Thus, for example, in the preparation of synthetic fibers, it is desirable that the fibers have a sticking temperature above about 150 C. and preferably about 200 C. Homopolymers of monomeric materials such as acrylonitrile, vinyl chloride and vinylidene chloride have been used, but it is often desirable to modify the properties of such polymers. In order to do this, attempts have been made to employ mixtures of polymeric materials, or to compound-plasticizers and similar compounding ingredients with the polymers, or to copolymerize the monomer with another monomer in order to modify the undesirable characteristics such as poor solubility and the like. In many cases, particularly with acrylonitrile polymers, attempts to form mixtures are difficult because of the incompatibility of thepolyacrylonitrile with other polymeric materials. This incompatibility often results in phase separation of the components as well as segmentation in fibers prepared from such mixtures. Although modified properties can be obtained by means of interpolymers, such as copolymers or terpolymers, the softening temperature of the copolymer is usually undesirably low.

It is accordingly an object of this invention to provide new and useful polymers containing N-Z-norcamphanylacrylamides alone or interpolymerized with one or more of the well known polymerizable olefinic monomers, including both the vinylic and/ or diolefinic monomers.

Another object of the invention is to provide new polymeric materials which are of particular utility in the manufacture of films, fibers, ShBCtS,'tl1bBS,' molded objectsand the like."

Another object of the invention is to provide polymers containing N-Z-norcamphanylacrylarhide or methacrylamide and characterized by having unusually high melting points and sticking temperatures.

Other objects will be apparent from the description and claims which follow.

These and other obiects are, attained by means of this invention, which comprises homopolymerizing a monomer of the formula in which R is either hydrogen or a methyl group, or copolymerizing-- either or-both of the monomers included within the structural formula with one or more olefinic monomers containing an ethylenic linkage. The polymers embodying the invention include homopolymers of 2 N-Z-norcamphanylacrylamide or N-2-norcamphanylmethacrylamide, as well as interpolymers with a vinylic monomer containing a single monoethylenic group of the struc ture CH=C and desirably a single CH2=C group, as well as interpolymers with diolefinic monomers characterized by a HC=F-C|2=CH1 group The N-2-norcamphanylacrylamides employed in practicing the invention can be readily prepared by reacting bicycloheptene with either acrylonitrile or methacrylonimile in the presence of sulfuric acid. The preparation of such monomers is described in detail in the copending application of Caldwell and Poe, Serial No. 446,956, filed July 30, 1954.

These compounds are normally solid materials which homopolymerize readily. The homopolymer of N-2-norcamphanylacrylamide has asticking temperature of -l50 C., andthe homopolymer of N-Z-norcamphanylmethacrylamide has a sticking temperature of C. Thus the-homopolymers canbe readily used for the preparation of films which have good optical properties and which are tough and high melting. They can also be used for the preparation of molded objects or sheets or tubes if desired. Although the homopolymers can be used in the preparation of synthetic fibers, fibers having most desirable properties are prepared from interpolymers of these monomerswith othervinylic or diolefinic monomers] Unlike most interpolymers, the copolymers of the norcamphanylacrylamide monomers with such materials as the vinylic and diolefinic monomers give products which have extremely high melting points. For example, when up to 20% by weight of norcamphanylaerylamide monomer is copolymerized with more than 80% by weight of acrylonitrile, the resulting copolymer has the desirable properties of polyacrylonitrile but can be dyed much more readiy than polyacrylonitrile and, in contrast to the usual copolymers, has a softening temperature in the vicinity of 200 C. Thus the noreamphanylacrylamide monomers function to modify the undesirable property of polyacrylonitrile as regardsdye aflinity without produc ing a copolymer having limited utility because of a low softening temperature. Similarly improved results are obtained by interpolymerizing a norcamphanylacrylamide monomer with any of the other vinylic or diolefinic monomers such as butadiene'and substituted butadienes, aro matic vinyl compounds such as styrene, vinyl halides such as vinylchloride andvinylidene chloride, acrylates, methacrylates, acrylarnides, methacrylamides, vinyl esters, yinyl ethers -vinyl ketones, vinylpyridines, maleamides,

"fuma'ramides, citraconarhides, itaconamides, maleamates,

fumaramates, .citraconamates, itaconarnates, ethylenic hydrocarbons'such as ethylene, acrylic acid, methacrylic acid, and similar well known olefin monomers. The norcamphanylacrylamides can be interpolymerized with one or more of such other olefinic monomers in any desired proportions from about 1% of the norcamphanylacrylamide component to about 99% of such component. Elastic or rubbery interpolymers are prepared using such diolefinic monomers as butadiene, isoprene, 2,3-dimethyl butadiene, 2-chloro butadiene, Z-cyano butadiene, 2-phenyl butadiene, and 2-acetoxy butadiene. I p

In practicing the invention, the copolymers of the nor camphanylacrylamide monomer with acrylonitrile or a-methylacrylonitrile are particularly useful. In addition to the copolymerizable olefinic monomers set out hereinabove, the diverse, character. of the vinylic and diolefinic monomers suitable for use in practicing the invention is illustrated by the fact that fiuoro derivatives such as vinyl fluoride, vinylidene fluoride, tetrafiuoroethylene and chloro-trifluoroethylene; N-vinyl imides,

N-vinyl lactarns, alkenyl esters such as isopropenyl acetate, and similar polymerizable monomers are all suitable for use. Highly useful monomers containing a CH=C group include the acrylamides (including methacrylamides), C4-C21 diamides of dicarboxylic acids of 4-5 carbon atoms'such as maleamides, fumaramides, itaconamides and citraconamides, C4-C17 ester-amides of dicarboxylic acids of 4-5 carbon atoms such as male "amates, fumararnates, citraconamates and itaconamates, vinyl esters of monocarboxylic acids, acrylates, vinyl pyridines, vinylic halides such as vinyl chloride and vinylidene chloride, aryl vinyls such as styrene, tit-methyl styrene, p-acetamino styrene, and a-acetoxy styrene, vinyl others such as ethyl vinyl ether and isopropyl vinyl ether, vinyl ketones such as isopropenyl methyl ketone, methyl vinyl ketone, ethyl vinyl ketone and ethyl isopropenyl ketone, unsaturated acids such as acrylic acid, methacrylic acid and the like, esters such as dimethyl maleate, diethyl maleate, diisopropyl maleate, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate and the like, as well as such other vinylic monomers as fumaronitrile, methacrylonitrile, N-vinyl phthalimide, ethylene and similar materials have a monoethylenic unsaturation.

As acrylamides, we can advantageously use in our invention those represented by the following general formula:

wherein R1 and R2 each represents a hydrogen atom or .an alkyl group containing from 1 to 4 carbon atoms (e. g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl,

etc., groups) and R4 represents a hydrogen atom or a methyl group. Typical acrylamides include, for example,

acrylamide, N-methylacrylamide, N-ethylacrylamide, N- isopropylacrylamide, N-n-butylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, methacrylamide, N- methylrnethacrylarnide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N,N-dimethylmethacrylamide, etc.

As maleamides, we can advantageously use those repf resented by the following general formula:

wherein R1 and R2 each have the values given above.

Typical maleamides include, for example, "maleamide, N-rnethylmaleamide, N-ethylmaleamide,' N-pr'opylmaleamide, N-isopropylmaleamide, 'N-n-butylmaleamide, N,N-dimethylmaleamide, N,N'-diethylmaleamide, N,N- di-n-butylmaleamide, N,N'-methylethylmaleamide, N,N- tetramethylmaleamide, N,N-tetraethylmaleamide, N,N- dimethyl-N,N'-diethylmaleamide, etc.

As fumaramides, we can advantageously use those represented by the following general formula:

As itaconamides, we can advantageously employ those represented by the following general formula:

wherein R1 and R2 each have the values given above. Typical itaconamides include, for example, itaconamide, N-methylitac0namide, N-ethylitaconamide, N-propylitaconamide, N,N-dimethylitaconamide, N,N'-diethylitaconamide, etc.

As citraconamides, we can advantageously employ those represented by the following general formula:

wherein R1 and R2 each have the values given above. Typical citraconacides include, for example, citraconamide, N-methylcitraconamide, N-ethylcitrac0namide, N-nbutylcitraconamide, N,N-dimethylcitraconamide, N,N'- diethylcitraconamide, the N,N-butylcitraconamides, N,N-tetramethylcitraconamide, etc.

The maleamates useful in practicing our invention comprise those represented by the following general formula:

wherein R1, R2 and Ra each have the values given above.

Typical are methyl fumaramate, ethyl fumaramate, propyl fumaramate,.n-butyl fumaramate, methyl N-methylfumaramate, ethyl N-methylfumaramate, the butyl N- methylfumaramates, methyl N-dimethylfumaramates,

ethyl N-dimethylfumaramates, n-butyl N-dimethylfumaramate, the methyl N-dibutylfumaramates, etc.

As itaconamates, we can advantageously employ those represented by the following general formulas:

I wherein R; R1 and R3 eachhave the valuesgiven above. Typical itaconamates include, for example, methyl itaconamate, ethyl itaconamate, propyl itaconamate, the

S butyl itaconamates, methyl N-m'etliylitaconamate, ethyl N-methylitaconamate, propyl N-methylitaconamate, n butyl N-methylitaconamate, methyl N-dimthylitaconamate, ethyl N-dimethylitaco-namate, nbutyl N-dimethylitaconamate, the methyl N-dibutylitaconamates, etc.

As citraconamates, we can advantageously employ those represented by the following general formulas:

o. CHrC-iL-OR;

cHr==c-d-'on;

wherein R3 has the values given above and R4 represents a hydrogen atom, a methyl group, or an ethyl group. Typical acrylates includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl m'ethacrylatc, propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, methyl ethacrylate, ethylethacrylate, etc.

As vinyl esters, we can advantageously employ those represented by the following general formula:

O CHF=CHO-J-Rc wherein R3 has the values given above.v Typical vinyl esters, include, for example, vinyl acetate, vinyl propionate, vinyl butyra'te, vinyl isobutyrate, etc.

The polymerization is advantageously carried out in an aqueous medium, although other reaction media, such as organic solvents, can be employed; for example, a polymerization medium consisting of aqueous acetone,

.or 'other aqueous solvent can ire-used, ,The polymerization. also. proceeds satisfactorily Yin ..rionaqu eous. systems such as in the lower alcohols, ket onesand esters, as well as in the aliphatic or aromatic hydrocarbons, dioxane, glycol monoethers, and the like. Mass or bulk-polymerization can also be used. H

The polymerizations can be accelerated by the use of a well known polymerization catalyst.-

Such catalysts: are

commonly used in the art of polymerization, and'our invention is not to be limited to any particular catalyst material. Catalysts which h'ave'been found to" be especially useful comprise the peroxide polymerization catalysts, such as the organic peroxides (e. g. benzoyl peroxide, acetyl peroxide, acetyl benzoyl peroxide, lauryl peroxide, oleoyl peroxide, triacetone peroxide, urea peroxide, t butyl hydroperoxide, alkyl'percarbonates, e tc:),

hydrogen'peroxide, perb'orates' (eifg'. alkali-metal perborates', such; as those of. sodium-and potassium, te) pe'r'sul'fate ('e. g-L anon metal ammonium persul-fate, etc=) Other-"catalysts such as" the kthz-ine's-a'iririS, etc.,"can' be used; 3 The quantity of catalystused' can be varied, de- 1 pending on the monomer, amount omit-dengue. F

The temperature of polymerization can be varied over the range of 20-130 C. depending upon the polymer being prepared, and temperatures of -60 C. are suitable in most cases. If desired, emulsifying agents can be added to the reaction mixture to distribute uniformly the reactants throughout the reaction medium. Typical emulsifying agents include the alkali metal salts of certain alkyl acid sulfates (e. g. sodium lauryl sulfate), alkali metal salts of aromatic sulfonic acids (sodium isobutylnaphthalenesulfonate), alkali metal or amine addition salts of sulfcsuccinic acid esters, alkali metal salts of fatty acids containing from 12 to 20 carbon atoms, sulfonated fatty acid amides, alkali metal salts of alkane sulfonic acids, sulfonated esters, etc.

I The polymerization can be carried out in the presence of chain regulators, such as hexyl, octyl, lauryl, dodecyl, myristyl mercaptans, etc., which impart improved solubility properties to the polymer compositions. If desired, reducing agents such as alkali metal bisulfites (e. g. potassium, sodium, etc., bisulfites) can be added to reduce the time required for the polymerization to be effected.

1 The homopolymers and copolymers prepared in accordance with this invention can be extruded by the usual methods to give films, rods, tubes and the like. Photographically useful films can also be cast from solution in accordance with usual practice and used as film base materials for either black-and-white or color films Wherein suitable emulsion layers are deposited on a supporting layer of the polymers of this invention. The polymers can also be dissolved in solvents and spun by wet or dry methods to give fibers. The compositions can also be molded by injection or compression methods to give a variety of molded objects.

In the manufacture of fibers, the copolymers are of particular utility since they have high sticking temperatures and good affinity for dyes. Thus, for example, when a norcamphanylacrylamide monomer is copolymerized with acrylonitrile or methacrylonitrile, particularly with the nitrile monomer predominating, the fibers possess the desirable characteristics of acrylouitrile fibers but with greatly enhanced dyeability and sticking temperatures in the vicinity of 200 C. Particularly useful copolymers comprise 80-99% acrylonitrile and 120% norcamphanylacrylamide. Other particularly useful fiberforrning copolymers comprise at least by weight of vinyl or vinylidene chloride with N-2-norcamphanylacrylamide or methacrylamide. Highly elastic. copolymers are formed with the butadiene monomers, and the products show excellent resistance to hydrocarbon solvents.

The homopolymers and copolymers embodying the invention can be prepared by either batch or continuous processes. The continuous processes can include continuous addition of either or both of the monomers, as weil as continuous removal of polymer if,desired., The polymers can 'theri be compounded with the usual compounding ingredients if desired including pigments, fillers, dyes, plasticizers and the like in' accordance with usual compounding practice. As with most synthetic fibers, the fibers prepared in accordance with this invention are desirably oriented by drafting at. elevated temperatures, and preferably the fibers are hot drawn and relaxed before use.

The invention is' illustrated by the following examples of certain preferred embodiments thereof, although it is not intended that the invention shall be limited by the illustrative embodiments unless otherwise specifically indicated.

Example 1.H0m0p0lymer of N(2-norcamphanyl) acrylamide and the solution was refluxed for 4 hours; The polymer separated fromsolution. It was washed with ace- "7 tone and dried to give a yield of 4.0 g. The product was soluble in methylene chloride and ethylene dichloride. Films stuck to the hot bar at 140-150" C.

Example 2.-Homp0lymer of N-(Z-norcamphanyl) methaerylamide Six g. of N-(2-norcamphanyl) methacrylamide and 0.06 g. benzoylperoxide were dissolved in 40 cc. of ter-butyl alcohol and the solution was held at 50 C. for 24 hours. A viscous solution was obtained. Films cast from the solution were clear and tough. They stuck to the hot bar at 170 C.

Example 3.H0mop0lymer of acrylamide N-(Z-norcamphanyl Example 4.lnterp0lymer of N-(2-n0rcamphanyl) acrylamide and acrylonitrile Twenty g. of acrylonitrile and 5 g. of N-(2-norcamphanyl) acrylamide were placed in a bottle and the following materials were added:

0.25 g. potassium persulfate 0.50 g. sodium octadecyl sulfate 0.05 g. ter-dodecyl mercaptan 200.0 cc. water The bottle was tumbled in a water bath at 50-55" C. for 20 hours. The product was coagulated with sodium sulfate, washed, and dried. It weighed 24 g. Analysis showed that it contained 20% of the N-(2-norcamphanyl) acrylamide. The product was soluble in dimethylformamide, dimethylacetamide, and 'y-butyrolactone. It was soluble in a mixture of 2 parts acetonitrile-l part dimethylformamide.

Ten parts of the interpolymer was dissolved in 40 parts dimethylformamide and the solution was extruded through a spinnerette into a precipitating bath composed of 70% water-30% dirnethylformamide. The filaments were washed with water and drafted 400% at 120-l30 C. The resulting fibers were strong and elastic. They stuck to the hot bar at 190 C. This is an unusually high sticking temperature for an acrylonitrile copolymer that contains 20% of a modifying monomer. The fibers dyed well with cellulose acetate dyes and acid wool dyes.

Example 5.lnterpolymer of N-(Z-noreamphanyl) melhacrylamide and acrylonitrile Example 6.-Interp0lymer of N-(Z-riorcamphanyl) acrylamide and acrylonitrile The following materials were placed in a bottle:

50.0 g. N-(2-norcamphanyl) acrylamide 50.0 g. acrylonitrile 1.0 g. azo-bis-isobutyronitrile 200.0 cc. ter-butyl alcohol The solution was heated at 50 C. for 24 hours. The product was filtered off, .washed. with methanol, and

.dried, to give a yield of 75 g.-, Analysis showed that it contained 53% acrylonitrile The product was soluble in acetonitrile. Films cast from the solution were clear and tough. They had a sticking temperature of l50155 C. The films are useful in photography.

Example 7.--Interpolymer of N-(z-norcamphanyl) acrylamide and methacrylonitrile The following materials were placed in a bottle:

10.0 g. N-(Z-norcamphanyl) acrylamide 20.0 g. methacrylonitrile 0.5 g. sodium dodecyl sulfate 0.3 g. sodium persulfate 200.0 cc. water The mixture was tumbled at 50 C. for 48 hours. washing and drying, the product weighed 26 g. useful as a molding plastic.

After It is Example 8.-Interp0lymer of N-(Z-norcamphanyl) acrylamide and vinyl chloride The following materials'were placed in an autoclave:

60.0 g. N-(2-norcamphanyl) acrylamide 40.0 g. vinyl chloride 2.0 g. sulfonated mineral oil 1.0 g. potassium persulfate 800.0 cc. water The mixture was stirred at 60 C. for 18 hours. A yield of 87 g. product was obtained. The interpolymer was soluble in cyclohexanone and gave clear, tough films that are useful as photographic film base.

Example 9.-Interp0lymer of N-(Z-norcamphanyl) methacrylamide and vinylidene chloride Using the method described in Example 8, an interpolymer was made from 80% vinylidene chloride and 20% N-(2-norcamphanyl) methacrylamide. The product was useful for the manufacture of fibers and bristles.

Example 10.-Interp0lymer '0f N-(Z-rwrcamphanyl) methacrylamide and methyl methacrylate A product having the composition 65% N-(2-norcamphanyl) mcthacrylamide-35% methyl methacrylate is useful as a molding plastic.

Example 11.-Interpolymer of N-(2-n0rcamphanyl) acrylamide and butadiene The following materials were placed in an autoclave: 25.0 g. N-(2-norcamphanyl) acrylamide 75.0 g. butadiene 3.0 g. soap 1.0 g. potassium persulfate 400.0 cc. water The mixture was stirred at 50-60" C. for 48 hours. The

'product is a rubber that shows improved resistance to hydrocarbon solvents.

Example 12.--lnterp0lymer of N-(Z-norcamphanyl) acrylamitie and diethyl fumarate .merize readily to useful products and interpolymerize in all proportions with-any of the olefinic monomers, and all such homopolymersand copolymers are within the wherein R is selected from the gen and methyl groups.

2. A homopolymer of N-Z-norcamphanylacrylamide. 3. A homopolymer of N-Z-norcamphanyhnethacrylamide. v g V p v 4. An interpolymer of a monomer or the formula wherein R is selected from the group consisting of hydrogen and methyl groups, with at least one other olefinic monomer selected from the group consisting of copolymerizable monoolefinic and diolefinic monomers.

5. A copolymer of a monomer of the formula H 1110 on,

wherein R is selected from the group consisting of hydrogen and methyl groups, and a copolymerizable vinylic monomer characterized by a single --CH=C group.

6. A copolymer of a monomer of the formula wherein R is selected from the group consisting of hydrogen and methyl groups, and a copolymerizable diolefinic monomer characterizedby a 7. A copolymer of a monomer of the formula H 0 \CHI l H: (I:

H-NH-C o-c=cn, L H

and a monomer of the formula om=c CN group consisting of hydro wherein each R is selected from the group consisting of hydrogen and methyl groups.

fi ly nier of a monomer of the formula v V HIC/ L HI I Hit H-NH=-C O-c=c wherein R is selected from the group consisting of hydrogen and methyl groups, and a monoethylenic chloride containing two carbon atoms.

9. A copolymer of a monomer of .the formula H wherein R is selected from the group consisting of hydrogen and methyl groups, and" a butadiene monomer-copolymerizable therewith. I

10. A copolymer of at least about by weight of acrylonitrile and not more than about 20% by weight of N-Z-norcamphanylacrylamide. I p

11. A copolymer of atleast about 80% by weight of acrylonitrile with up to about 20% by weight of N-2- norcamphanylmethacrylamide.

12,, A copolymer of at least 50% by weight of acrylonitrilewith amonomer of the formula v I wherein R is selected from the group consisting of hydrogen and methyl groups.

13. A copolymer of N-Z-norcamphanylacrylamide and butadiene.

14. The method which comprises polymerizing in the presence of a polymerization catalyst a monomer of the formula wherein R is selected from the group consisting of hydrogen and methyl groups.

15. The method which comprises interpolymerizing in the presence of a polymerization catalyst a dispersion of a monomer of the formula wherein R is selected from the group consisting of hydrogen and methyl groups, and a copolymerizable olefinic monomer.

16. The method which comprises copolymerizing in the presence of a polymerization catalyst a dispersion of a monomer of the formula 1 1 wherein R. is selected from the group consisting of hydrogen and "methyl groups and a copolymerizable 'vinylic monomer characterized by a single -CH=C group.

17. The method which comprises copolymerizing in the presence of a polymerization catalyst a dispersion of a monomer of the formula 11 mo on,

wherein R is selected from the group consisting of hydrogen and methyl groups, and a copolymerizable diolefinic monomer characterized by a wherein R is selected from the group consisting of hydrogen and methyl groups.

19. The method whichcomprises polymerizing in a dispersion and in thepres'ence of a polymerization catalyst a mixture of a monomer of the formula wherein R is selected from the group consisting of hydrogen and methyl groups, and a monoethylenic chloride containing two carbon atoms.

20. The method which comprises polymerizing in a dispersion and in the presence of a polymerization catalyst a mixture of butadiene and a monomer of the formula Hi (IJH CH: U mo (bH-NH-co-o=cm wherein R is selected from the group consisting of hydrogen and methyl groups.

References Cited in the file of this patent UNITED STATES PATENTS 2,653,975 Mowry et a1. Sept. 29, 1953 

1. THE REACTION PRODUCT OF 3,5-DIISOPHROPYLMONOMER OF THE FORMULA 